Linear free energy relationship of the energy of the CTTS transition of Halide ions with the solvatochromic parameter α |
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Authors: | Dean C Luehrs Richard E Brown Kalpana A Godbole |
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Institution: | (1) Department of Chemistry and Chemical Engineering, Michigan Technological University, 49931 Houghton, MI;(2) Department of Mathematical Sciences, Michigan Technological University, 49931 Houghton, MI |
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Abstract: | A linear free energy relationship was found betweenv
max, the energy of the absorption maximum of chloride, bromide, or iodide ion in various solvents, and the solvatochromic parameter which is a measure of the hydrogen bond donor ability of the solvent. The relationships are: for chloride,v
max=6.99 +50.16 kK; for bromide,v
max=5.52 +45.20 kK; for iodide,v
max=5.02 +40.33 kK. The correlation ofv
max for iodide ion with gave a larger correlation coefficient and smaller standard deviation than a correlation with the E
T
(30) parameter of Dimroth. From the values ofv
max for iodide ion and the solvated electron in liquid ammonia at 25°C, these correlations indicate a preliminary value of 0.00 for the parameter of liquid ammonia. This had not been reported before and is lower than expected from a general knowledge of the physical and chemical properties of liquid ammonia but is consistent with a more detailed consideration and recent gas phase measurements of hydrogen bond donor strength. |
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Keywords: | Halide ions solvent effects charge transfer to solvent solvatochromic parameters |
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